CN113817123A - Novel polyurethane and application thereof - Google Patents

Novel polyurethane and application thereof Download PDF

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CN113817123A
CN113817123A CN202110877818.1A CN202110877818A CN113817123A CN 113817123 A CN113817123 A CN 113817123A CN 202110877818 A CN202110877818 A CN 202110877818A CN 113817123 A CN113817123 A CN 113817123A
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perovskite
spiro
ethyl acetate
novel polyurethane
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CN113817123B (en
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姜月
徐冬冬
麦润昇
王茹
高进伟
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South China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a novel polyurethane, which has the structure shown as the following formula (I):
Figure DDA0003188197480000011
wherein:
Figure DDA0003188197480000012
the polyurethane synthesis process is simple, the cost is low, and when the polyurethane is applied to a perovskite solar cell, the surface defects of perovskite can be reduced, and the hole mobility can be improved, so that the efficiency of a perovskite device is improved. The invention also discloses application of the novel polyurethane in perovskite photoelectric devices, and the novel polyurethane is used for perovskite sunIn the field of energy batteries, the perovskite solar battery can have higher wet stability and water stability, and lead leakage can be inhibited to a certain extent.

Description

Novel polyurethane and application thereof
Technical Field
The invention belongs to the technical field of perovskite photoelectric devices, and particularly relates to novel polyurethane and application thereof.
Background
The non-renewable energy is being consumed continuously, the human society faces a severe energy crisis and the environmental pressure generated thereby, and the development of green renewable energy technology is imminent. Solar energy is an inexhaustible renewable energy source. Although the traditional solar cell based on inorganic semiconductor materials such as silicon and the like is commercialized, the application of the traditional solar cell is limited due to the defects that the production process is complex, the cost is too high, and the inorganic materials are not degradable and are not easy to flexibly process.
In recent years, lead-perovskite halide solar cells (PSCs) have the advantages of solution processability, low defect density, low cost, high yield, and the like, and have become a third-generation photovoltaic technology with great development prospects. With unprecedented development, the power conversion efficiency of small-area PSCs has exceeded 25%, while large perovskite modules are also rapidly increasing.
Perovskite solar cells continue to face obstacles in the way of commercialization as an emerging high efficiency, low cost photovoltaic technology. In recent years, the primary factors that determine commercialization of perovskite photovoltaic technology have shifted from solar cell performance to stability, reproducibility, device upgrade, and prevention of module lead leakage over the device lifetime. The potential risk of lead leakage when using perovskite solar cells in integrated photovoltaics can be considered as an environmental and public health risk. Therefore, improving the stability of the perovskite solar cell and the problem of lead leakage is an important assistance for promoting the commercialization of the perovskite.
Disclosure of Invention
The invention aims to provide novel polyurethane, which has the advantages of simple synthesis process and low cost, and can reduce the surface defects of perovskite and improve the hole mobility when being applied to perovskite solar cells, thereby improving the efficiency of perovskite devices.
The invention also aims to provide application of the novel polyurethane in perovskite photoelectric devices, and the novel polyurethane is used in the field of perovskite solar cells, so that the perovskite solar cells have higher moisture stability and water stability, and lead leakage can be inhibited to a certain extent.
The first object of the present invention can be achieved by the following technical solutions: a novel polyurethane having the structure shown in formula (I):
Figure BDA0003188197460000021
wherein:
Figure BDA0003188197460000022
preferably, the novel polyurethanes of the present invention are curing insoluble novel polyurethanes.
Preferably, the novel polyurethanes of the present invention are prepared primarily by reacting a spirobifluorene-hydroxy reactive functional group chemical (spirooh), having the formula shown below in formula (II), with an isocyanate:
Figure BDA0003188197460000023
the isocyanate is 1, 4-benzene diisocyanate, 1, 5-naphthalene diisocyanate and 4, 4' -methylene bis (phenyl isocyanate); 4, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, 1, 3-phenylene diisocyanate or hexamethylene diisocyanate.
Wherein: 4, 4' -methylenebis (phenyl isocyanate); the structural formulas of 4, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, 1, 3-phenylene diisocyanate and hexamethylene diisocyanate are respectively as follows:
Figure BDA0003188197460000031
thus, in particular, the novel polyurethane may have the structure:
Figure BDA0003188197460000032
or:
Figure BDA0003188197460000033
or:
Figure BDA0003188197460000034
or:
Figure BDA0003188197460000041
or:
Figure BDA0003188197460000042
or:
Figure BDA0003188197460000043
and the like.
Preferably, the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) is a hydroxyl active functional group compound containing tetrahydroxy micromolecule with spirobifluorene and diphenylamine structures.
Preferably, the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) is prepared by the following method:
(1) selecting raw materials of glycols and phosphorus tribromide, adding the glycols into a reaction vessel, cooling a salt bath, adding the phosphorus tribromide, heating to 140-180 ℃, stirring for reaction for 2-4 hours, and obtaining a product a by using a column chromatography after the reaction is finished;
(2) selecting a product a and 3, 4-dihydro-2H-pyran (DHP), adding the product a and 3, 4-dihydro-2H-pyran into a reaction container, adding dichloromethane, stirring for dissolving, adding p-toluenesulfonic acid, stirring for 5-12H at room temperature, and after the reaction is finished, obtaining a product b by using a column chromatography;
(3) selecting a product b and aniline, adding the product b, aniline, potassium carbonate and N, N-Dimethylformamide (DMF) into a reaction container, heating and stirring for reaction for 24-36 h, and after the reaction is finished, performing column chromatography to obtain a product c;
(4) selecting a product c and 2,2 ', 7, 7' -tetrabromo-9, 9 '-spirobifluorene, adding the product c and the 2, 2', 7,7 '-tetrabromo-9, 9' -spirobifluorene into a reaction vessel, and adding sodium tert-butoxide and Pd2(dba)3Stirring tri-tert-butylphosphine tetrafluoroborate and toluene, carrying out reflux reaction at 90-110 ℃ for 24-36 h, and carrying out column chromatography to obtain a product d after the reaction is finished;
(5) and (3) dissolving the product d in Tetrahydrofuran (THF), adding methanol and p-toluenesulfonic acid, stirring at room temperature for 8-18 h, adjusting the pH to be neutral by using a sodium carbonate aqueous solution after the reaction is finished, adding ethyl acetate, extracting by using deionized water, drying by using anhydrous sodium sulfate, and obtaining the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) by using a column chromatography method.
In the spirobifluorene-hydroxyl reactive functional group chemical (Spiro-OH):
preferably, the diol in the step (1) is diethylene glycol, 1, 3-propylene glycol or dipropylene glycol, and the molar ratio of the diol to the raw material phosphorus tribromide is 7-10: 1; the mobile phase adopted in the column chromatography in the step (1) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1.5-3: 1.
More preferably, the diol in the step (1) is diethylene glycol, the molar ratio of the diethylene glycol to the phosphorus tribromide is 8.7: 1, the diethylene glycol is heated to 160 ℃, the mixture is stirred and reacts for 2 hours, and the mobile phase adopted in the column chromatography is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 2: 1.
Wherein the structural formulas of the 1, 3-propanediol and the dipropylene glycol are as follows:
Figure BDA0003188197460000051
preferably, the molar ratio of the product a to the p-toluenesulfonic acid in the step (2) is 80-120: 1.
Preferably, the mobile phase adopted in the column chromatography in the step (2) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 10-20.
More preferably, the molar ratio of the product a to the p-toluenesulfonic acid in the step (2) is 100: 1; the mobile phase adopted in the column chromatography in the step (2) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 12.
Preferably, the molar ratio of the product b to the aniline in the step (3) is 1: 1-3.
Preferably, the mobile phase adopted in the column chromatography in the step (3) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 4-6.
More preferably, the molar ratio of the product b to the aniline in the step (3) is 1: 1; the mobile phase adopted in the column chromatography in the step (3) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 4.
Preferably, the 2,2 ', 7,7 ' -tetrabromo-9, 9 ' -spirobifluorene in the step (4): and (c) product c: sodium tert-butoxide, Pd2(dba)3The molar ratio of the compound to the tri-tert-butylphosphine tetrafluoroborate is as follows: 1: 4.4-7: 2-4: 0.03-0.1: 0.03-0.6; and (4) adopting ethyl acetate and petroleum ether as mobile phases in the column chromatography in the step (4), wherein the volume ratio of the ethyl acetate to the petroleum ether is 1: 1.5-2.
More preferably, the 2,2 ', 7,7 ' -tetrabromo-9, 9 ' -spirobifluorene in the step (4): and (c) product c: sodium tert-butoxide, Pd2(dba)3The molar ratio of the compound to the tri-tert-butylphosphine tetrafluoroborate is as follows: 1: 6: 2.6: 0.04: 0.0425; the mobile phase adopted in the column chromatography in the step (4) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 2.
Preferably, the molar ratio of the product d to the p-toluenesulfonic acid in the step (5) is 1: 4-6, the volume ratio of the tetrahydrofuran to the methanol is 1: 3-5, and the mobile phase adopted in the column chromatography in the step (5) is ethyl acetate and methanol, and the volume ratio of the ethyl acetate to the methanol is 1: 15-20.
More preferably, the molar ratio of the product d to the p-toluenesulfonic acid in the step (5) is 1: 4, the volume ratio of the tetrahydrofuran to the methanol is 1: 4, and the mobile phase used in the column chromatography in the step (5) is ethyl acetate and methanol, and the volume ratio of the ethyl acetate to the methanol is 1: 20.
Preferably, the novel polyurethane is prepared by mixing spirobifluorene-hydroxyl active functional group chemical (spiroo-OH) and isocyanate in a solvent (such as chlorobenzene and toluene), and then stirring at 70-95 ℃ (preferably 85 ℃) for a prepolymerization reaction for 6-12 h (preferably 8h) to synthesize the novel polyurethane spiroo-PU.
The second object of the present invention can be achieved by the following technical solutions: the novel polyurethane is applied to perovskite photoelectric devices, the perovskite photoelectric devices comprise perovskite solar cells, each perovskite solar cell comprises a transparent substrate layer, an electron transport layer, a perovskite active layer, an interface layer, a hole transport layer and a metal electrode layer, and the interface layer is novel polyurethane (Spiro-PU).
Preferably, the transparent substrate layer is transparent conductive glass FTO.
Preferably, the material of the electron transport layer is SnO2And a thickness of about 20 nm.
Preferably, the perovskite active layer material is lead methylamine iodide, and the general chemical structure formula is CH3NH3PbI3The thickness is 400 to 500 nm.
Preferably, the interface layer of the present invention is made of a novel polyurethane (Spiro-PU) with a thickness of about 100 nm.
Preferably, the material of the hole transport layer of the present invention is 2,2 ', 7,7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 ' -spirobifluorene (Spiro-OMeTAD) with a thickness of 150-200 nm.
Preferably, the metal electrode layer is made of silver and has a thickness of 60-100 nm.
Experiments show that the obtained Spiro-OH is subjected to crosslinking reaction with isocyanate to generate novel polyurethane (Spiro-PU), and then the polyurethane is spin-coated on the interface of the perovskite to obtain a crosslinking and curing interface coating.
Experiments show that the obtained Spiro-OH is subjected to crosslinking reaction with isocyanate to generate novel polyurethane (Spiro-PU), the polyurethane is spin-coated on the interface of perovskite, a crosslinking and curing interface coating can be obtained, the novel polyurethane (Spiro-PU) interface has higher tightness, and the amide group generated by the reaction can effectively complex lead ions and effectively prevent lead leakage.
Preferably, the perovskite photoelectric device comprises perovskite photoelectric fields such as a perovskite light emitting diode, a perovskite X-ray detector, a perovskite laser, a perovskite solar cell and the like. For application to perovskite solar cells, perovskite can be made to have higher moisture stability and water stability, and lead leakage can be suppressed to some extent.
Therefore, the application of the novel polyurethane (Spiro-PU) is the application of the novel polyurethane (Spiro-PU) in improving the water stability and the moisture stability of the perovskite solar cell, and the application of the novel polyurethane (Spiro-PU) in reducing lead leakage caused in the process of using the perovskite solar cell.
Thus, the novel polyurethanes of the present invention are high density crosslinked insoluble films. The film is suitable for perovskite photoelectric fields such as perovskite light emitting diodes, perovskite X-ray detectors, perovskite lasers, perovskite solar cells and the like. Wherein, in the perovskite solar cell field, carbonyl in Spiro-PU is reacted with Pb2+Chemical bond combined passivation of under-coordinated Pb2+Defects, the combination of amino and iodide inhibits ion migration, and the three-dimensional net-shaped acyl amine with high crosslinking density increases the electron density, further enhances the passivation effect of the three-dimensional net-shaped acyl amine and greatly improvesThe efficiency of the cell. When the thickness of the Spiro-PU film is about 100nm, the extraction of photogenerated carriers is not inhibited, the hole mobility can be improved, and the high activity of NCO groups can be matched with H2And (3) O reaction is carried out, the crosslinking density is further improved, and the Spiro-PU terminated by NCO has better damp-heat stability as a moisture-proof layer. And the film also exhibits an excellent positive effect of inhibiting lead leakage. This strategy gives perovskite devices with superior PCE, excellent humidity, thermal, water and long-term stability, and effectively reduces lead contamination. Furthermore, flexible perovskite solar cells using Spiro-PU retain significant stability over long periods of time in terms of resistance to mechanical bending due to interfacial contact and adhesion. The novel polyurethane provided by the invention provides a new idea for improving the efficiency of the perovskite solar cell, improving the stability and reducing lead leakage, and is expected to be applied to industrial production.
Compared with the prior art, the invention has the following beneficial effects:
(1) the interface material has simple synthesis steps, low cost and wide raw material source, can be prepolymerized in various solvents, has higher glass transition temperature and higher hole mobility after being solidified, can passivate defects, improves the perovskite efficiency, and can obtain higher open-circuit Voltage (VOC) and Fill Factor (FF), so that CH (carbon-oxygen) is obtained3NH3PbI3The perovskite solar cell efficiency of the system exceeds 21 percent;
(2) because the interface material has better tightness, crosslinking insolubility and hydrophobicity, the moisture stability and the water stability of the perovskite solar cell can be greatly improved;
(3) the obtained Spiro-OH is subjected to crosslinking reaction with isocyanate to generate novel polyurethane (Spiro-PU), the interface of the novel polyurethane (Spiro-PU) has higher leakproofness, and an amide group generated by the reaction can effectively complex lead ions, so that lead leakage is effectively prevented;
(4) the novel polyurethane (Spiro-PU) obtained by the crosslinking reaction has high controllability mainly because the diol raw materials in the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) can be selected from diethylene glycol, 1, 3-propylene glycol or dipropylene glycol and the like according to requirements, and the isocyanate can be selected from 1, 4-benzene diisocyanate, 1, 5-naphthalene diisocyanate and 4, 4' -methylene bis (phenyl isocyanate); 4, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, 1, 3-phenylene diisocyanate or hexamethylene diisocyanate and the like, so that novel polyurethanes (Spiro-PU) with different molecular weights and different types can be obtained.
Drawings
FIG. 1 is a scheme for synthesizing a product a1 in example 1;
FIG. 2 shows the NMR spectrum of product a1 in example 1(1H NMR)；
FIG. 3 is a scheme for synthesizing the product b1 in example 1;
FIG. 4 is the NMR spectrum of product b1 in example 1 (C:)1H NMR)；
FIG. 5 is a scheme for synthesizing the product c1 in example 1;
FIG. 6 is the NMR spectrum of product c1 in example 1 (C)1H NMR)；
FIG. 7 is a scheme for synthesizing the product d1 in example 1;
FIG. 8 shows the NMR spectrum of product d1 in example 1(1H NMR)；
FIG. 9 is a synthetic route to Spiro-OH in example 1;
FIG. 10 shows the Spiro-OH NMR spectrum of the product of example 1: (1H NMR)；
FIG. 11 is a high resolution mass spectrum of Spiro-OH in example 1;
FIG. 12 is a synthetic route of novel polyurethane Spiro-PU (P-PU and N-PU) of the interface material of example 1;
FIG. 13 is an infrared characterization of the novel polyurethane Spiro-PU (P-PU and N-PU) of the interface material of example 2;
FIG. 14 is a J-V characteristic curve for a device based on two different PU interface materials in example 3;
FIG. 15 is a moisture stability, XRD characterization of the interfacial material polyurethane PU (P-PU and N-PU) of example 3;
FIG. 16 is a photograph of the water stability of the interface material polyurethane PU (P-PU and N-PU) in example 3;
FIG. 17 is a lead leakage characterization of the interface material polyurethane PU (P-PU and N-PU) of example 3;
FIG. 18 is a diagram showing a process for preparing a novel polyurethane Spiro-PU as an interface material in accordance with an embodiment;
FIG. 19 is a structural formula of a novel polyurethane Spiro-PU of the interface material in example 2;
FIG. 20 is a structural formula of a novel polyurethane Spiro-PU of the interface material in example 2;
FIG. 21 is a structural formula of a novel polyurethane Spiro-PU of an interface material in example 4;
FIG. 22 is a structural formula of a novel polyurethane Spiro-PU of an interface material in example 5;
FIG. 23 is the structural formula of the novel polyurethane Spiro-PU of example 6 as an interface material;
FIG. 24 shows the structure of a novel polyurethane Spiro-PU as an interface material in example 7.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The novel polyurethane provided by the invention has the structure shown as the following formula (I):
Figure BDA0003188197460000101
wherein:
Figure BDA0003188197460000102
the novel polyurethane is mainly prepared by reacting spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) with isocyanate, and the synthetic route is shown as a figure 18, wherein the structural formula of the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) is shown as the following formula (II):
Figure BDA0003188197460000103
the isocyanate is 1, 4-benzene diisocyanate, 1, 5-naphthalene diisocyanate and 4, 4' -methylene bis (phenyl isocyanate); 4, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, 1, 3-phenylene diisocyanate or hexamethylene diisocyanate.
The preparation of spirobifluorene-hydroxy reactive functional group chemicals (Spiro-OH) is illustrated below using diethylene glycol and 1, 4-phenylene diisocyanate, 1, 5-naphthalene diisocyanate as examples:
example 1
The preparation of spirobifluorene-hydroxyl reactive functional group chemical (Spiro-OH) comprises the following steps:
1. synthesis and characterization of product a 1:
(1) phosphorus tribromide (3.15g, 11.5mmol) was slowly added dropwise to diethylene glycol (10.6g, 100mmol) at-5 ℃ for more than 0.5h, the reaction mixture was slowly heated to room temperature and to 160 ℃ for 2 hours;
(2) after the reaction was completed, purification was performed by column chromatography (ethyl acetate: petroleum ether, volume ratio): 2: 1) to obtain an oily product a1 with a yield of 48% (8g, 47.6 mmol).
The synthetic route of the product a1 is shown in figure 1, and the nuclear magnetic resonance hydrogen spectrum of the product a1(1H NMR) as shown in fig. 2, the NMR hydrogen spectrum characterization data is as follows:1H NMR(600MHz，CDCl3-d1)：4.19(s，1H)，3.70-3.56(m，8H)。
2. synthesis and characterization of product b 1:
(1) selecting a product a1(7.06g, 42mmol) and 3, 4-dihydro-2H-pyran (DHP, 3.87g, 46mmol), adding the product a1 and the 3, 4-dihydro-2H-pyran into a reaction vessel, adding dichloromethane (70mL) into the reaction vessel, stirring the mixture to dissolve the mixture, then adding p-toluenesulfonic acid (72mg,0.42mmol), and stirring the mixture at room temperature for 8 hours;
(2) after the reaction, the reaction mixture was washed with deionized water, evaporated under reduced pressure, and purified by column chromatography (ethyl acetate: petroleum ether) ═ 1: 12, oily product b1 was obtained in 53% yield (4g, 15.9 mmol).
The synthetic route of the product b1 is shown in FIG. 3, and the nuclear magnetic resonance hydrogen spectrum of the material b1 (R) ((R))1H NMR) as shown in fig. 4, the nuclear magnetic resonance characterization data is as follows:1H NMR(600MHz，CDCl3-d1)：4.54(s，1H)，3.77-3.40(m，10H)。
3. synthesis and characterization of product c 1:
(1) aniline (1.48g, 15.9mmol) was dissolved in DMF (10mL) and placed in a round bottom flask, after which product b1(4g, 15.9mmol) and K were added2CO3(5.5g, 40 mmol). Then, the reaction mixture was heated to 70 ℃ and stirred for 36 h;
(2) after the reaction, the solvent was removed by rotary evaporation under reduced pressure, and CHCl was used2The crude product was extracted 3 times and the organic layer was dried over anhydrous sodium sulfate;
(3) the crude product was purified by column chromatography on silica gel using ethyl acetate/petroleum ether (1: 4) as eluent to give c1 as a yellow liquid in 72% yield (3g, 11.3 mmol).
The synthetic route of the product c1 is shown in FIG. 5, and the nuclear magnetic resonance hydrogen spectrum of the product c1 (R) ((R))1H NMR) as shown in fig. 6, the nuclear magnetic resonance hydrogen spectrum characterization data is as follows:1H NMR(600MHz，CDCl3-d1)：7.22-7.19(t，J＝12Hz，2H)，6.74-6.65(m，3H)，4.67-4.66(t，J＝6Hz，1H)，3.92-3.32(m，10H)，1.86-1.55(m，6H)。
4. synthesis and characterization of product d 1:
(1) 2,2 ', 7, 7' -dibromo-9, 9-spirobifluorene (0.5g, 0.8mmol), product c1(1.27g, 4.8mmol), sodium tert-butoxide (t-BuONa) (0.2g, 2.08mmol), Pd2(dba) were added to a Schlenk reaction tube3(0.03g, 0.032mmol), tris (tert-butyl) phosphine tetrafluoroborate (0.01g, 0.034mmol), dry toluene (10ml) was added and the reaction was heated at 105 ℃ under a nitrogen atmosphere for 24 hours;
(2) after the reaction is finished, extracting with dichloromethane and water, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering and concentrating;
(3) the crude product was purified by silica gel column (ethyl acetate: petroleum ether ═ 1: 2) to give (Spiro-ET) as a yellow oil d1(600mg, yield 55.4%).
The synthetic route of the product d1 is shown in FIG. 7, and the nuclear magnetic resonance hydrogen spectrum of the product d1 (R) ((R))1H NMR) as shown in fig. 8, the NMR hydrogen spectrum characterization data is as follows:1H NMR(600MHz，CDCl3-d1)：7.57-7.56(d，J＝6Hz，1H)，7.14-7.12(t，J＝12Hz，2H)，7.05-7.04(d，J＝6Hz，1H)，6.84-6.83(d，J＝6Hz，1H)，6.80-6.77(t，J＝12Hz，2H)，6.56(s 1H)，4.57-4.55(t，J＝12Hz，1H)，3.81-73.74(m，4H)，3.60-3.44(m，6H)，1.78-1.48(m，6H)。
5. and (3) synthesizing and characterizing a product, namely Spiro-OH:
(1) product d1(500mg, 0.36mmol), tetrahydrofuran 3mL, 12mL methanol and p-toluenesulfonic acid (252mg, 1.46mmol) were stirred at room temperature for 12 h;
(2) after the reaction, Na is added2CO3The aqueous solution was adjusted to neutral pH, extracted three times with ethyl acetate and column chromatographed on silica gel (ethyl acetate: methanol 15: 1) to afford a yellow-green solid (230mg, 61% yield).
The synthetic route of the product Spiro-OH is shown in FIG. 9, and the nuclear magnetic resonance hydrogen spectrum of the product Spiro-OH is shown in (A)1H NMR) as shown in fig. 10, the nuclear magnetic resonance hydrogen spectrum characterization data is as follows:1h NMR (600MHz, DMSO-d 6): 7.71 to 7.69(d, J ═ 6Hz, 1H), 7.14 to 7.11(t, J ═ 18Hz, 2H), 7.05 to 7.03(d, J ═ 12Hz, 1H), 6.84 to 6.80(M, 3H), 6.34(s, 1H), 4.52 to 4.50(t, J ═ 12Hz, 1H), 3.76 to 3.74(t, J ═ 12Hz, 2H), 3.48 to 3.46(t, J ═ 12Hz, 2H), 3.77 to 3.75(t, J ═ 12Hz, 2H), 3.28 to 3.26(t, J ═ 12Hz, 2H), to which the peak positions and the number of hydrogens correspond, the structure of the material Spiro-OH can be determined. The high resolution mass spectrum of the material Spiro-OH is shown in fig. 11, and the structural correctness is further confirmed by mass spectrum.
Example 2
Preparation and characterization of polyurethane cyclone-PU:
Spiro-OH and 1, 4-phenylene diisocyanate (PPDI)/1, 5-Naphthalene Diisocyanate (NDI) were mixed in a chlorobenzene solution, and then the prepolymerization was stirred at 85 ℃ for 8 hours. The synthetic route of the polyurethane synthesized by PPDI is called P-PU, NDI is called N-PU, and the synthetic route of the polyurethane which is P-PU or N-PU is shown in figure 12, and the structural formula is shown in figure 20 or figure 19.
To characterize the formation of the polyurethane, this is illustrated by FTIR, as shown in fig. 13. NCO-terminated PU prepolymer at 2266cm-1There is an absorption peak corresponding to the-NCO group. The characteristic peaks of the polyurethane groups appear at 3336cm-1And 1718cm-1Here, stretching vibration corresponding to N-H group and C ═ O group, respectively, and — OH bond in Spiro-OH was 3446cm-1The stretching vibration of (b) disappears.
Example 3
Perovskite solar cell prepared by using compound Spiro-PU
(1) Preparation of Electron transport layer solution SnCl2·2H2O was dissolved in 20mL butanol (2 mL water) to give 0.1M SnCl2·2H2And (4) O solution. SnCl2·2H2Refluxing O solution for 2-4 hours at 110 ℃ by using an open reflux device to synthesize SnO2And (4) nano suspension.
(2) Preparing an electron transport layer, spin-coating the prepared electron transport layer solution in the step (1) on cleaned conductive glass FTO, wherein the spin-coating process is 1000r/min 3s and then 3000r/min 30s, and then annealing at 150 ℃ for 60 minutes;
(3) preparing a mixed solution of lead iodide and iodomethylamine of a perovskite active layer precursor solution, wherein the mass ratio of the lead iodide to the iodomethylamine is generally 1: 0.8-1.15, a solvent is a mixed solution of N-N-dimethylformamide and dimethyl sulfoxide, and the volume ratio is generally 7: 3 or 4: 1;
(4) preparing a perovskite active layer, namely spin-coating perovskite precursor liquid on the conductive glass coated with the electron transmission layer in the step (2), wherein the spin-coating process is 800r/min 3s and then 4000r/min 30s, 400 microliter of chlorobenzene is dropwise added in the spin-coating process to serve as an anti-solvent, and then annealing is carried out for 10-15 minutes at 100 ℃;
(5) preparing a perovskite thin film of a Spiro-PU interface layer obtained in the step (4), heating the perovskite thin film to 85 ℃, and spin-coating Spiro-PU precursor liquid (obtained by preparation in the embodiment 2) on the perovskite thin film, wherein the spin-coating process is 1000r/min 3s and then 3000r/min 30 s;
(6) preparing a hole transport layer, and spin-coating a Spiro-OMeTAD solution on the PU film spin-coated in the step (5), wherein the spin-coating process is 100r/min 3s and then 3000r/min 30 s;
(7) and (3) evaporating a silver electrode on the surface of the cavity transmission layer in the step (6) by using a thermal evaporation method.
As shown in FIG. 14, the improved perovskite efficiency with PU was significantly improved compared to the unmodified perovskite, for CH3NH3PbI3Perovskite of the system, the efficiency of which exceeds 21%, the voltage (V)oc) There is a significant increase in Fill Factor (FF) as a result of PU passivating the surface defects and increasing hole mobility.
As shown in fig. 15, in order to illustrate the moisture resistance improvement of the perovskite according to the present invention, the perovskite thin film coated with PU and uncoated with PU is placed at a humidity of 85%, and it is obvious that Spiro-PU greatly improves the moisture stability of the perovskite through surface macroscopic change and XRD detection. And it can be seen from XRD that the perovskite modified by polyurethane only has the peak of perovskite hydrate, and lead iodide does not appear, which provides possibility for self-repairing of perovskite.
In order to show the compactness of the Spiro-PU and the water stability of the perovskite modified by the Spiro-PU, as shown in fig. 16, the perovskite modified by the PU still maintains a black phase in water for a long time by directly soaking the perovskite in water, which is a great improvement of the water stability of the perovskite. Meanwhile, the lead pollution in the perovskite is a great problem threatening the life safety of people and the environmental pollution, and when the perovskite is soaked in water for a long time, the perovskite coated by PU is decomposed into PbI2And MAI, the lead iodide is firmly anchored below the polyurethane interface, rather than dissolving in water. That is, in this invention, under dense coverage of Spiro-PU, the amide groups effectively complex pb2+As shown in FIG. 17, it can be seen from the atomic absorption measurement that lead in perovskite was effectively coated under polyurethane after water immersion for up to three hours, and the aqueous solution contained almost no Pb2+Meanwhile, the yellow film coated by PU is just lead iodide through XRD measurement. This is to prevent leadA very effective way for pollution provides a new idea for the problem of perovskite lead pollution, and has higher practical significance and production value.
Based on CH only as described above3NH3PbI3The research of the perovskite of the system has higher positive effects on ternary, binary, all-inorganic and tin-based perovskites. Meanwhile, the positive effect of the poly PU is not limited to a perovskite solar cell system, but is applicable to the whole perovskite photoelectric field, including perovskite light emitting diodes, perovskite X-ray detectors, perovskite lasers, perovskite solar cells and other perovskite photoelectric fields.
Example 4
In contrast to example 1, the isocyanate was 4, 4 '-diisocyanato-3, 3' -dimethylbiphenyl. The structural formula is shown in figure 21.
Example 5
In contrast to example 1, the isocyanate was 4, 4' -methylenebis (phenyl isocyanate). The structural formula is shown in figure 22.
Example 6
In contrast to example 1, the isocyanate was 1, 3-phenylene diisocyanate. The structural formula is shown in figure 23.
Example 7
In contrast to example 1, the isocyanate was hexamethylene diisocyanate. The structural formula is shown in figure 24.
The above embodiments illustrate various embodiments of the present invention in detail, but the embodiments of the present invention are not limited thereto, and those skilled in the art can achieve the objectives of the present invention based on the disclosure of the present invention, and any modifications and variations based on the concept of the present invention fall within the scope of the present invention, which is defined by the claims.

Claims (10)

1. A novel polyurethane is characterized in that: the structure of the compound is shown as the following formula (I):
Figure FDA0003188197450000011
wherein:
Figure FDA0003188197450000012
2. the novel polyurethane of claim 1, wherein: the novel polyurethane is mainly prepared by reacting spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) with isocyanate, wherein the structural formula of the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) is shown as the following formula (II):
Figure FDA0003188197450000013
the isocyanate is 1, 4-benzene diisocyanate, 1, 5-naphthalene diisocyanate and 4, 4' -methylene bis (phenyl isocyanate); 4, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, 1, 3-phenylene diisocyanate or hexamethylene diisocyanate.
3. The novel polyurethane of claim 2, wherein: the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) is prepared by the following method:
(1) selecting raw materials of glycols and phosphorus tribromide, adding the glycols into a reaction vessel, cooling a salt bath, adding the phosphorus tribromide, heating to 140-180 ℃, stirring for reaction for 2-4 hours, and obtaining a product a by using a column chromatography after the reaction is finished;
(2) selecting a product a and 3, 4-dihydro-2H-pyran (DHP), adding the product a and 3, 4-dihydro-2H-pyran into a reaction container, adding dichloromethane, stirring for dissolving, adding p-toluenesulfonic acid, stirring for 5-12H at room temperature, and after the reaction is finished, obtaining a product b by using a column chromatography;
(3) selecting a product b and aniline, adding the product b, aniline, potassium carbonate and N, N-Dimethylformamide (DMF) into a reaction container, heating and stirring for reaction for 24-36 h, and after the reaction is finished, performing column chromatography to obtain a product c;
(4) selecting a product c and 2,2 ', 7, 7' -tetrabromo-9, 9 '-spirobifluorene, adding the product c and the 2, 2', 7,7 '-tetrabromo-9, 9' -spirobifluorene into a reaction vessel, and adding sodium tert-butoxide and Pd2(dba)3Stirring tri-tert-butylphosphine tetrafluoroborate and toluene, carrying out reflux reaction at 90-110 ℃ for 24-36 h, and carrying out column chromatography to obtain a product d after the reaction is finished;
(5) and (3) dissolving the product d in Tetrahydrofuran (THF), adding methanol and p-toluenesulfonic acid, stirring at room temperature for 8-18 h, adjusting the pH to be neutral by using a sodium carbonate aqueous solution after the reaction is finished, adding ethyl acetate, extracting by using deionized water, drying by using anhydrous sodium sulfate, and obtaining the spirobifluorene-hydroxyl active functional group chemical (Spiro-OH) by using a column chromatography method.
4. A novel polyurethane according to claim 3, characterized in that: in the step (1), the diol is diethylene glycol, 1, 3-propylene glycol or dipropylene glycol, and the molar ratio of the diol to the raw material phosphorus tribromide is 7-10: 1; the mobile phase adopted in the column chromatography in the step (1) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1.5-3: 1.
5. A novel polyurethane according to claim 3, characterized in that: the molar ratio of the product a to the p-toluenesulfonic acid in the step (2) is 80-120: 1; the mobile phase adopted in the column chromatography in the step (2) is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1: 10-20.
6. A novel polyurethane according to claim 3, characterized in that: the molar ratio of the product b to the aniline in the step (3) is 1: 1-3; and (3) adopting ethyl acetate and petroleum ether as mobile phases in the column chromatography in the step (3), wherein the volume ratio of the ethyl acetate to the petroleum ether is 1: 4-6.
7. Novel polyurethane according to claim 3, characterized in thatThe method comprises the following steps: the 2,2 ', 7,7 ' -tetrabromo-9, 9 ' -spirobifluorene in the step (4): and (c) product c: sodium tert-butoxide, Pd2(dba)3The molar ratio of the compound to the tri-tert-butylphosphine tetrafluoroborate is as follows: 1: 4.4-7: 2-4: 0.03-0.1: 0.03-0.6; and (4) adopting ethyl acetate and petroleum ether as mobile phases in the column chromatography in the step (4), wherein the volume ratio of the ethyl acetate to the petroleum ether is 1: 1.5-2.
8. A novel polyurethane according to claim 3, characterized in that: the molar ratio of the product d to the p-toluenesulfonic acid in the step (5) is 1: 4-6, the volume ratio of the tetrahydrofuran to the methanol is 1: 3-5, and the mobile phase adopted in the column chromatography in the step (5) is ethyl acetate and methanol, and the volume ratio of the ethyl acetate to the methanol is 1: 15-20.
9. Use of a novel polyurethane according to any one of claims 1 to 8 in perovskite opto-electrical devices characterised in that: the perovskite photoelectric device comprises a perovskite solar cell, the perovskite solar cell comprises a transparent substrate layer, an electron transport layer, a perovskite active layer, an interface layer, a hole transport layer and a metal electrode layer, and the interface layer is made of novel polyurethane (Spiro-PU).
10. The use according to claim 9, wherein: the application refers to the application of the novel polyurethane (Spiro-PU) in improving the water stability and the moisture stability of the perovskite solar cell, and the application refers to the application of the novel polyurethane (Spiro-PU) in reducing lead leakage caused in the use process of perovskite solar cell.
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